Refractory material and product thereof containing low-silica electrofused magnesia clinker

ABSTRACT

Disclosed herein are a refractory material of high-purity electrofused magnesia clinker having good resistance to corrosion by slag, especially the slag with a high iron content, at high temperatures under an oxidative environment, and a burned or unburned refractory brick made of such refractory material of high corrosion resistance, which is superior in corrosion resistance as well as spalling resistance. 
     The refractory material comprises more than 10 wt. % of electrofused magnesia clinker containing 98.0 to 99.8 wt. % of MgO, less than 0.05 wt. % of SiO 2 , and 0.1 to 2.0 wt. % of CaO. It may be in the form of burned or unburned or prepared unshaped refractories.

FIELD OF ART

The present invention relates to a refractory material of magnesia clinker and to an application thereof.

BACKGROUND OF THE INVENTION

Magnesia-carbon bricks composed mainly of MgO have been in general use as a lining material for converters and stainless steel manufacturing furnaces on account of their good spalling and slag resistance.

They are still subject to slag attack when used in an environment where the refining temperature is higher and secondary combustion prevails. This results in the dissolution of the magnesia clinker in slag, leaving the carbon, such as graphite, in bricks always exposed with the surfaces of the bricks. This accelerates the carbon oxidation and, hence, the rate of corrosion.

A conventional way to protect graphite in magnesia-carbon bricks from oxidation is the addition of an antioxidant of a readily oxidizable metal to the brick constituents.

However, an additional antioxidant alone is not enough to prevent the dissolution and oxidation of decarburization layer resulting from a slag attack in refining furnaces operating at 1700° C. or above.

Concerning the improvement of slag corrosion resistance at high temperatures, Japanese Patent Publication No. Sho 54-8206 discloses that electrofused magnesia is superior to sintered magnesia in resistance to corrosion by molten metal and slag when used as a raw material in refractories for steel and non-ferrous metal melting furnaces, because of its power crystal boundaries where mechanical destruction and chemical corrosion begin.

As a raw material of filler for lining refractories for steel and nonferrous metal melting furnaces, electrofused magnesia is used in the form of a grain having a size of 5 to 3 mm, 3 to 1 mm, or 1 to 0 mm, obtained by crushing clinker ingots, which are subjected to classification and particle size regulation.

For electrofused clinker to be a strong filler for refractories, the electrofused magnesia should include a high ratio of single crystal. Clinker ingot with a large ratio of single crystal can be obtained by melting from high-purity magnesia containing more than 99.9 wt. % of MgO. However, this kind of high-purity magnesia is too expensive to be used as a refractory material, so its use is limited to optical windows and electronic device substrates.

A possible means to obtain electrofused magnesia with a high ratio of single crystal is by the electrofusion of a relatively less pure raw material containing 99.0 to 99.8 wt. % of magnesia to obtain clinker ingots from which large crystals are selectively chosen. However, this method is deemed impractical because of low yields.

Meanwhile, it is known that electrofused magnesia used as a filler of refractories exhibits good corrosion resistance because CaO crystallizes out at the grain boundary of the periclase crystal having a high CaO/SiO₂ ratio and reacts with slag to increase its viscosity, thereby preventing its infiltration into the grain boundary.

However, electrofused magnesia with a high CaO/SiO₂ ratio has the disadvantage of limiting the growth of single crystal by increased impurities. Moreover, the addition of CaO to electrofused magnesia poses a problem associated with the slaking of CaO which deteriorates the structure of refractories.

It is an object of the present invention to provide electrofused magnesia clinker having a high ratio of single crystal which is obtained from a raw material of comparatively low purity which has never before been thought to be usable as well as a refractory material of electrofused magnesia having a high CaO/SiO₂ ratio.

It is another object of the present invention to provide a refractory material containing electrofused magnesia clinker which is stable against slag attack and especially has high corrosion resistance against slag with a high iron content, even in an oxidative environment at high temperatures.

It is yet another object of the present invention to provide a refractory material of electrofused magnesia clinker which poses no problems associated with the slaking of CaO when the electrofused magnesia material contains CaO for improving corrosion resistance through the ability of CaO to prevent the infiltration of slag into the grain boundary.

It is a further object of the present invention to provide a burned or unburned refractory brick or a prepared unshaped refractory of good Corrosion and spalling resistance which is produced from highly corrosion-resistant electrofused magnesia clinker.

DISCLOSURE OF THE INVENTION

In general, magnesia clinker in magnesia-carbon bricks begins to deteriorate upon deterioration at the grain boundary. Namely, a foreign matter infiltrates inside of the brick by infiltration of silicate or silicate containing iron oxide into the grain boundary, which accelerates the following reaction to magnesia to form a low-melting material, leading to the disintegration of bricks.

    2MgO+SiO.sub.2 →2MgO·2SiO.sub.2

    MgO+FeO→(Mg, Fe)O

It was found that impurities hinder the growth of periclase crystals generating as the temperature of molten magnesia goes down in the production of electrofused magnesia clinker. Particularly, MgO is the most important factor to inhibit the crystal growth. This finding led to the idea of using magnesia clinker having a higher ratio of single crystal than ordinary magnesia clinker produced from high-purity magnesia. Using magnesia clinker having a higher ratio of single crystal prevents the deterioration at the grain boundaries and the formation of low-melting materials which cause the disintegration of bricks.

The present invention is embodied in a refractory material of electrofused magnesia clinker containing 98.0 to 9.8 wt. % of MgO, less than 0.05 wt. %, preferably less than 0.02 wt. %, more preferably less than 0.01 wt. % of SiO₂, and 0.1 to 2.0 wt. % of CaO, with the CaO/SiO₂ ratio being high, and also having a markedly high ratio of single crystal in grains of ordinary size for refractory use.

According to the present invention, this electrofused magnesia clinker can be made into burned or unburned refractory bricks with good corrosion resistance upon incorporation with more than 10 wt. % of other refractory materials.

SiO₂ contained with CaO in the electrofused magnesia material forms CaO-SiO₂ compounds in the early stages of the production of electrofused magnesia material, reducing the effectiveness of the free CaO which should prevent the infiltration of slag into the crystal grain boundary.

Moreover, the presence of CaO in an electrofused magnesia material cannot exhibit the effective function in periclase crystals. In other words, CaO effectively operates when reacting with slag which is infiltrating into the grain boundary. Therefore, the presence of CaO should be concentrated into the crystal grain boundary.

In order to concentrate CaO into the crystal grain boundary, when periclase crystals crystalize from molten magnesia for producing an electrofused magnesia material, the periclase crystals should be purified driving CaO, as impurities, toward the crystal grain boundary.

The inventors of the present invention found that the presence of SiO₂ is the most important factor to prevent the pure growth of periclase crystals. In the present invention, reduction of the SiO₂ content provides the refractory materials in which CaO can be concentrated into the crystal grain boundary, and further provides a burned or unburned refractory brick as well as unshaped refractory for pouring or stamp use.

In addition thereto, according to the present invention, the low SiO₂ content promotes the pure growth of periclase crystals, giving rise to electrofused magnesia ingots having a much larger crystal size than ordinary ones of the same magnesia content.

The high ratio of single crystal means the presence of fewer grain boundaries where mechanical disruption and chemical corrosion take place. This leads to improved corrosion resistance against slag and molten metal. In addition, the high CaO/SiO₂ ratio drives CaO out of the periclase crystals to the grain boundary of the polycrystalline electrofused magnesia filler. The CaO on the grain boundary reacts with slag, increasing its viscosity, to prevent its infiltration into the crystals. This also leads to improved corrosion resistance.

According to the present invention, the electrofused magnesia should contain 98.0 to 99.8 wt. % of MgO. With an MgO content below 98.0 wt. %, the electrofused magnesia will relatively contain too many impurities to allow the smooth growth of periclase crystals from molten magnesia. Hence the resulting electrofused magnesia lacks its fundamental characteristic properties owing to insufficient crystal size. With an MgO content more than 99.8 wt. %, the electrofused magnesia will not contain a sufficient amount of CaO.

According to the present invention, the electrofused magnesia should contain less than 0.05 wt. % of SiO₂. Otherwise, the excess SiO₂ will react with CaO to form CaOSiO₂ compounds in the early stages of the production of electrofused magnesia. This reaction decreases the amount of free CaO to be driven to the grain boundary where it will prevent the infiltration of slag. Therefore, the SiO₂ content should be as low as possible, preferably, lower than 0.03 wt. %, more preferably lower than 0.02 wt. %.

According to the present invention, the electrofused magnesia should contain 0.1 to 2.0 wt. % of CaO. CaO in an amount below 0.1 wt. % will not be enough to prevent the infiltration of slag into the grain boundary through its reaction with slag which causes slag to increase in viscosity. In addition, such a small amount of CaO is insufficient to form MgO.CaO which exists as a solid solution in the low temperature range from room temperature to 700° C., and CaO phase is crystalized in periclase structure, leading to poor resistance of the grain itself against thermal shocks. The desirable CaO content is from 0.2 wt. % to 1.0 wt. %. With a CaO content in excess of 2.0 wt. %, the electrofused magnesia will have poor corrosion resistance because CaO functions as an undesirable impurity. In addition, excess CaO hinders the growth of periclase crystals during the production of clinker. An adequate amount of CaO in the specified range does not pose any problems associated with slaking.

According to the present invention, the electrofused magnesia may be incorporated with a variety of refractory materials, including carbonaceous powder such as natural or artificial graphite, coke, mesophase carbon, carbon black, and diamond powder, ordinary magnesia clinker, electrofused maglime clinker containing 1.5 to 40 wt. % of CaO, other sintered clinker, dolomite clinker filler, and a refractory material selected from zirconia, zircon, alumina, silica, chromium mineral, silicon carbide, BN, and B₄ C as well as any combination thereof.

Among them, the incorporation of industrial diamond powder into the appropriate working portion of the refractories can lead to the best use of the mechanical advantage of diamond such as high oxidation resistance, high hardness and high strength. Thus, the finished bricks containing industrial diamond powder are desirable to be used for the refractories for controlling flows such as the tuyere and sliding nozzle which require high oxidation and wear resistance.

The magnesia clinker to be used as a filler in the present invention may be obtained by electrofusing a raw material of magnesia such as sintered magnesia, calcined magnesia, magnesium hydroxide, and magnesium carbonate. These refractory raw materials should preferably have as high a degree of crystallinity as possible. These raw materials may also be incorporated with pitch or phenolic polymer resin powder to improve spalling resistance.

The electrofused magnesia is made into refractory bricks with the aid of a binder selected from phenolic resin, furan resin, epoxy resin, modified phenolic resin, melamine resin, and urea resin. A phenolic resin or modified phenolic resin is more desirable from the view point of residual carbon and price.

The refractory bricks may be incorporated with a powder of metal or alloy thereof such as Al, Si, Ca, Cr, Mg, and B to improve the oxidation resistance, corrosion resistance, and high temperature strength.

Magnesia clinker of the above-mentioned composition will exhibit its effect regardless of the type of refractory materials--carbon-free burned and unburned bricks, carbon-containing burned and unburned bricks, and prepared unshaped refractories.

Incidentally, the amount of carbonaceous powder to be incorporated into the refractory bricks should be from 3 wt. % to 40 wt. %. An amount below the lower limit will not be enough to produce satisfactory spalling and slag resistance. An amount in excess of the upper limit will result in difficulty in mixing, poor operation and low oxidation resistance.

DESCRIPTION OF THE PREFERRED EMBODIMENT EXAMPLE 1

Table 1 shows the various characteristics of electrofused magnesia prepared from different raw materials. Each electrofused magnesia was prepared from ordinary sintered raw materials in different ratios and electrofused.

                                      TABLE 1                                      __________________________________________________________________________     Composition   Composition of                                                   of raw material (wt. %)                                                                      electrofused magnesia (wt. %)                                                                 Ratio of single crystal in                        MgO  CaO                                                                               SiO.sub.2                                                                         B.sub.2 O.sub.3                                                                   MgO CaO SiO.sub.2                                                                         B.sub.2 O.sub.3                                                                    electrofused magnesia (%)                         __________________________________________________________________________     1A                                                                               99.40                                                                             0.55                                                                              0.01                                                                              0.005                                                                             99.44                                                                              0.50                                                                               0.01                                                                              0.004                                                                              79.2                                              1B                                                                               99.15                                                                             0.71                                                                              0.07                                                                              0.035                                                                             99.18                                                                              0.67                                                                               0.05                                                                              0.032                                                                              71.4                                              1C                                                                               99.48                                                                             0.27                                                                              0.12                                                                              0.006                                                                             99.50                                                                              0.24                                                                               0.08                                                                              0.006                                                                              32.7                                              __________________________________________________________________________      Note:                                                                          The electrofused magnesia clinker ingots obtained from each raw material       was crushed into grains and classified into a grain size of 5 to 3 mm, 3       to 1 mm, and 1 to 0 mm. Then, the ratio by weight of single crystal of th      grains of 5 to 3 mm was calculated.                                      

In the above Table 1, samples 1A and 1B are examples of the present invention, and sample C is a comparative example. It is to be noted that samples 1A and 1B pertaining to the present invention have a higher ratio of single crystal than sample 1C for the purpose of comparison.

10 mm×10 mm×60 mm of each samples cut out of the ingots of the electrofused materials shown in Table 1, in conjunction with three additional comparative examples 1D to 1F, underwent four kinds of corrosion resistance tests. The results are shown in Table 2 below.

                  TABLE 2                                                          ______________________________________                                                                  Corrosion resistance                                  Chemical compo-                                                                               Ratio of  (melt loss index)*                                    sition (wt. %) single    Test   Test Test Test                                 Sample                                                                               MgO    SiO.sub.2                                                                             CaO  crystal (%)                                                                            1    2    3    4                              ______________________________________                                         1A    99.44  0.01   0.50 79.2    72   71   69   71                             1B    99.18  0.05   0.67 71.4    76   73   74   73                             1E    98.52  0.03   1.38 36.5    100  100  100  100                            1D    99.91  0.02   0.04 81.1    95   92   90   92                             1C    99.50  0.08   0.24 32.7    97   95   96   95                             1F    99.37  0.22   0.35 21.3    108  105  105  110                            ______________________________________                                          *Note:                                                                         The corrosion resistance tests were performed on samples measuring 10          × 10 × 60 mm cut out of electrofused magnesia ingots.              Test 1: Dipping in molten slag having a CaO/SiO.sub.2 ratio of 1.2 at          1600° C. for 15 minutes in an induction furnace.                        Test 2: Dipping in molten slag having a CaO/SiO.sub.2 ratio of 2.0 at          1600° C. for 15 minutes in an induction furnace.                        Test 3: Dipping in molten slag having a CaO/SiO.sub.2 ratio of 3.0 at          1600° C. for 15 minutes in an induction furnace.                        Test 4: Dipping in molten mill scale at 1600° C. for 15 minutes in      an induction furnace.                                                    

It is noted in Table 2 that samples 1A and 1B pertaining to the present invention are far superior in corrosion resistance to the comparative samples 1C to 1F. Thus the electrofused magnesia of thee present invention can be used as a filler for refractory materials of any type--shaped or unshaped, burned or unburned--to impart good corrosion resistance.

EXAMPLE 2

The chemical compositions of the electrofused magnesia clinker used in this example are shown in Table 3. Sample 2A is in accordance with the present invention, and samples 2E, 2D, 2C and 2I do not fall in the scope of the present invention.

                  TABLE 3                                                          ______________________________________                                                  (wt. %)                                                               Sample     MgO    CaO         SiO.sub.2                                                                           B.sub.2 O.sub.3                             ______________________________________                                         2A         99.44  0.50        0.01 0.004                                       2E         98.52  1.38        0.03 0.032                                       2D         99.91  0.04        0.02 0.006                                       2C         99.50  0.24        0.08 0.006                                       2I         82.77  12.00       0.02 0.050                                       ______________________________________                                    

Each sample of electrofused magnesia clinker shown in Table 3 was made into unburned refractory materials according to the formulation shown in Table 4, by mixing, drying at 90° C. for 24 hours, and hardening at 250° C. for 10 hours.

In Table 4, samples 25 and 26 were further burned at 1000° C. in a reducing atmosphere.

Samples 21 and 24 contains 10 wt. % of electrofused magnesia according to the present invention. Samples 22 and 23 are examples in which mesophase carbon or diamond powder is respectively added to the formulation containing electrofused magnesia of the present invention. Samples 25 and 26 are examples of the burned products.

Refractory materials for comparison containing electrofused magnesia clinker samples 2C to 2I out of the present invention in the amount which does not fall into the scope of the present invention were prepared as shown in Table 5. These comparative examples underwent the same treatment as in the above and the properties thereof are also shown in Table 5.

Sample 26 is a comparative example in which the abovementioned unburned refractory was further burned at 1000° C. in a reducing atmosphere.

Comparative samples 21, 22, 23, 24 and 25 are unburned refractories which are inferior in corrosion resistance because they contain none or insufficient amount of the electrofused magnesia pertaining to the present invention.

Comparative sample 26, which is a burned one containing none of the electrofused magnesia Pertaining to the present invention, is inferior in corrosion resistance to sample 25 in Example which contains the electrofused magnesia as specified in the present invention.

Corrosion resistance (1) to (4) shown in Tables 4 and 5 is expressed in terms of index, with that of comparative example 1 being 100. It was determined by measuring the weight which the specimen had lost after immersion in a melting bath at 1600° C. for 15 minutes, heated by a high-frequency induction furnace. The content in the melting bath was slag (CaO/SiO₂ =1.2) for Test 1, slag (CaO/SiO₂ =2.0) for Test 2, slag (CaO/SiO₂ =3.0) for Test 3, and mill scale for Test 4.

                  TABLE 4                                                          ______________________________________                                         Example No.                                                                             21*     22*     23*   24*   25**  26**                                ______________________________________                                         Composition                                                                    (wt. %)                                                                        Electrofused                                                                            50      50      10    86    50    10                                  magnesia A                                                                     Electrofused                                                                            24              25          24    25                                  magnesia E                                                                     Electrofused             41                42                                  magnesia D                                                                     Electrofused                                                                   magnesia C                                                                     Electrofused     24                                                            magnesia I                                                                     Carbonaceous                                                                   power                                                                          Natural  20      15      15    10    20    18                                  graphite                                                                       Mesophase        5                                                             carbon                                                                         Diamond                  3                                                     power                                                                          Metallic 3       3       3     2     3     3                                   aluminum                                                                       Organic  3       3       3     2     3     2                                   binder                                                                         Characteristic                                                                 properties                                                                     Bulk density                                                                            2.84    2.84    2.85  2.89  2.78  2.78                                Apparent 3.8     3.7     3.7   3.6   1.5   1.8                                 porosity (%)                                                                   Compressive                                                                             421     430     441   461   320   380                                 strength                                                                       (kg/cm.sup.2)                                                                  High-    128     131     139   140   130   140                                 temperature                                                                    flexural                                                                       strength                                                                       (kg/cm.sup.2)                                                                  Corrosion                                                                               93      85      80    89    93    83                                  resistance                                                                     (1) index                                                                      Corrosion                                                                               89      87      82    83    90    90                                  resistance                                                                     (2) index                                                                      Corrosion                                                                               86      87      86    81    88    80                                  resistance                                                                     (3) index                                                                      Corrosion                                                                               93      95      93    89    90    88                                  resistance                                                                     (4) index                                                                      ______________________________________                                          *Unburned                                                                      **Burned                                                                 

                  TABLE 5                                                          ______________________________________                                         Example No.                                                                             21*     22*     23*   24*   25*   26**                                ______________________________________                                         Composition                                                                    (wt. %)                                                                        Electrofused                                                                            4                                                                     magnesia 2A                                                                    Electrofused                                                                            70      74                                                            magnesia 2E                                                                    Electrofused             74                74                                  magnesia 2D                                                                    Electrofused                   74                                              magnesia 2C                                                                    Electrofused                         74                                        magnesia 2I                                                                    Carbonaceous                                                                   power                                                                          Natural  20      20      20    20    20    20                                  graphite                                                                       Mesophase                                                                      carbon                                                                         Diamond                                                                        power                                                                          Metallic 3       3       3     3     3     3                                   aluminum                                                                       Organic  3       3       3     3     3     3                                   binder                                                                         Characteristic                                                                 properties                                                                     Bulk density                                                                            2.82    2.85    2.97  2.86  2.84  2.85                                Apparent 3.9     4.0     3.6   3.7   3.8   1.9                                 porosity (%)                                                                   Compressive                                                                             410     420     468   438   412   395                                 strength                                                                       (kg/cm.sup.2)                                                                  High-    125     120     146   132   124   140                                 temperature                                                                    flexural                                                                       strength                                                                       (kg/cm.sup.2)                                                                  Corrosion                                                                               100     98      111   121   100   99                                  resistance                                                                     (1) index                                                                      Corrosion                                                                               100     110     107   112   103   130                                 resistanct                                                                     (2) index                                                                      Corrosion                                                                               100     103     103   106   116   122                                 resistance                                                                     (3) index                                                                      Corrosion                                                                               100     99      108   136   127   102                                 resistance                                                                     (4) index                                                                      ______________________________________                                          *Unburned                                                                      **Burned                                                                 

Tables 4 and 5 clearly indicate that the samples of the present invention are far superior to the comparative samples in the melt loss index regardless of whether they are burned or not.

EXAMPLE 3

Specimens, measuring 10 mm×10 mm×60 mm, cut out of electrofused magnesia ingots of different composition, underwent four kinds of corrosion resistance tests and a slaking test conforming to the method of Japan Society for the Promotion of Science. The results are shown in Table 6.

                  TABLE 6                                                          ______________________________________                                                                        Slaking                                         Chemical       Corrosion resistance                                                                           resistance                                      composition    (melt loss index)*                                                                             (index)                                         (wt. %)        Test   Test   Test Test Increase in                             Sample                                                                               MgO    CaO    SiO.sub.2                                                                           1    2    3    4    weight**                          ______________________________________                                         3J    99.73  0.21   0.02 57   57   56   57   108                               3K    99.44  0.45   0.01 58   55   56   57   132                               3L    98.89  0.90   0.01 63   59   62   62   147                               3M    98.11  1.71   0.02 65   63   62   64   149                               3N    99.84  0.11   0.02 100  100  100  100  100                               3O    99.37  0.31   0.22 112  107  108  110   87                               3P    98.52  1.38   0.05 91   90   90   91   153                               3Q    97.51  2.25   0.41 93   95   93   94   429                               ______________________________________                                          * Specimens, measuring 10 mm × 10 mm × 60 mm, cut out of           electrofused magnesia ingots underwent corrosion resistance tests.             Test 1: Dipping in molten slag having a CaO/SiO.sub.2 ratio of 1.2 at          1600° C. for 15 minutes in an induction furnace.                        Test 2: Dipping in molten slag having a CaO/SiO.sub.2 ratio of 2.0 at          1600° C. for 15 minutes in an induction furnace.                        Test 3: Dipping in molten slag having a CaO/SiO.sub.2 ratio of 3.0 at          1600° C. for 15 minutes in an induction furnace.                        Test 4: Dipping in molten mill scale at 1600° C. for 15 minutes in      an induction furnace.                                                          **The slaking resistance test was performed on grains of 3.36 to 1.00 mm       in size obtained by the crushing of electrofused magnesia, followed by         classification. This test conforming to the method of Japan Society for        the Promotion of Science consists of heating the specimen in an autoclave      at 130 to 136° C. for 3 hours under 5 atms.                       

It is noted from Table 6 that samples 3J to 3M of the present invention are far superior to comparative samples 3N to 3Q in corrosion resistance without causing any problem in slaking resistance. These data suggest that the electrofused magnesia pertaining to the present invention can be made into refractory materials of any kind, burned or unburned, shaped or unshaped.

EXAMPLE 4

The bricks shown in Table 8 below were prepared from electrofused magnesia clinker each containing CaO and SiO₂ as shown in Table 7. Samples 4R and 4S accord with the present invention, and samples 4T and 4U are magnesia clinker out of the scope of the present invention.

                  TABLE 7                                                          ______________________________________                                         Sample           CaO    SiO.sub.2                                              ______________________________________                                         4R               1.38   0.018                                                  4S               0.21   0.018                                                  4T               0.31   0.220                                                  4U               2.12   0.018                                                  ______________________________________                                    

                                      TABLE 8                                      __________________________________________________________________________     Example No.          41* 42* 43* 44* 45* 46**                                                                               47**                              __________________________________________________________________________     Composition (wt. %)                                                            Electrofused magnesia 4R                                                                            50  50  50  10  10  50  50                                Electrofused magnesia 4S                                                                            24  24  24          24  36                                Electrofused magnesia 4T     2                                                 Electrofused magnesia 4U         64  15                                        Electrofused maglime clinker         50                                        Carbonaceous power                                                             Natural graphite     20  15  15  20  20  20  10                                Mesophase carbon         5                                                     Diamond power                3                                                 Metallic aluminum    3   3   3   3   2   3   2                                 Organic binder       3   3   3   3   3   3   2                                 Characteristic properties                                                      Bulk density         2.87                                                                               2.86                                                                               2.86                                                                               2.86                                                                               2.85                                                                               2.80                                                                               2.81                              Apparent porosity (%)                                                                               3.7 3.7 3.7 3.7 3.8 6.7 6.6                               Compressive strength (kg/cm.sup.2)                                                                  440 452 462 432 415 442 450                               High-temperature flexural strength (kg/cm.sup.2)                                                    136 145 140 131 115 138 141                               Corrosion resistance (1) index                                                                      93  88  92  96  88  88  86                                Corrosion resistance (2) index                                                                      88  87  85  92  94  87  86                                Corrosion resistance (3) index                                                                      84  82  83  87  109 84  87                                Corrosion resistance (4) index                                                                      80  78  79  89  104 78  84                                __________________________________________________________________________      *Unburned                                                                      **Burned                                                                       (1) Dipping in molten slag having a CaO/SiO.sub.2 ratio of 1.2 at              1600° C. for 15 minutes in an induction furnace.                        (2) Dipping in molten slag having a CaO/SiO.sub.2 ratio of 2.0 at              1600° C. for 15 minutes in an induction furnace.                        (3) Dipping in molten slag having a CaO/SiO.sub.2 ratio of 3.0 at              1600° C. for 15 minutes in an induction furnace.                        (4) Dipping in molten mill scale at 1600° C. for 15 minutes in an       induction furnace.8                                                      

Each formulation of Table 8 is selected from each electrofused magnesia clinker shown in Table 7, and basic refractory bricks are obtained by friction molding with the aid of an adequate amount of liquid phenolic binder, followed by drying at 90° C. for 24 hours and hardening at 250° C. for 10 hours. Samples 46 and 47 are further burned at 1000° C. in a reducing atmosphere.

Samples 41 and 44 contain more than 10 wt. % of electrofused magnesia. Samples 42 and 43 contain mesophase carbon or diamond powder, respectively.

Sample 45 contains more than 10 wt. % of electrofused magnesia in an electrofused maglime clinker material. Samples 46 and 47 are burned products.

Comparative compositions containing, as raw materials, electrofused magnesia clinker samples 4T and 4U in Table 7, out of the present invention, in the amount which does not fall into the scope of the present invention were prepared as shown in Table 9. These comparative examples underwent the same treatment as in the above and the properties thereof are also shown in Table 9. Comparative sample f in Table 9 shows an example of a burned brick.

                  TABLE 9                                                          ______________________________________                                         Example No.                                                                             a*      b*      c*    d*    e*    f**                                 ______________________________________                                         Composition                                                                    (wt. %)                                                                        Electrofused                                                                            4       4       50    30    4                                         magnesia 4R                                                                    Electrofused             42    23                                              magnesia 4S                                                                    Electrofused                                                                            70                          20                                        magnesia 4T                                                                    Electrofused     70                        74                                  magnesia 4U                                                                    Electrofused                         50                                        maglime                                                                        clinker                                                                        Carbonaceous                                                                   power                                                                          Natural  20      20      2     40    20    20                                  graphite                                                                       Mesophase                                                                      carbon                                                                         Diamond                                                                        power                                                                          Metallic 3       3       3     3     2     3                                   aluminum                                                                       Organic  3       3       2     4     3     3                                   binder                                                                         Characteristic                                                                 properties                                                                     Bulk density                                                                            2.86    2.87    3.02  2.79  2.84  2.80                                Apparent 3.8     3.8     3.1   4.8   3.9   6.9                                 porosity (%)                                                                   Compressive                                                                             430     420     490   460   410   419                                 strength                                                                       (kg/cm.sup.2)                                                                  High-    132     125     170   78    108   135                                 temperature                                                                    flexural                                                                       strength                                                                       (kg/cm.sup.2)                                                                  Corrosion                                                                               100     99      131   140   92    97                                  resistance                                                                     (1) index                                                                      Corrosion                                                                               100     100     123   133   99    99                                  resistanct                                                                     (2) index                                                                      Corrosion                                                                               100     109     120   125   118   100                                 resistance                                                                     (3) index                                                                      Corrosion                                                                               100     102     130   121   119   97                                  resistance                                                                     (4) index                                                                      ______________________________________                                          *Unburned                                                                      **Burned                                                                       Corrosion resistance:                                                           (1) Dipping in molten slag having a CaO/SiO.sub.2 ratio of 1.2 at             1600° C. for 15 minutes in an induction furnace.                        (2) Dipping in molten slag having a CaO/SiO.sub.2 ratio of 2.0 at              1600° C. for 15 minutes in an induction furnace.                        (3) Dipping in molten slag having a CaO/SiO.sub.2 ratio of 3.0 at              1600° C. for 15 minutes in an induction furnace.                        (4) Dipping in molten mill scale at 1600° C. for 15 minutes in an       induction furnace.                                                       

It is noted that comparative samples a, b, c, d and e provide a corrosion resistance that is inferior to the samples pertaining to the present invention because they contain non or insufficient electrofused magnesia, or because they contain carbonaceous powder in an insufficient or excessive amount.

It is noted that comparative sample f, which is a burned sample not containing the electrofused magnesia pertaining to the present invention, provides a corrosion resistance that is inferior to Sample 46 containing the electrofused magnesia as specified in the present invention.

These data suggest that the refractory materials pertaining to the present invention are superior in corrosion resistance in terms of melt loss index, whether they are burned or unburned.

EXAMPLE 5

This example demonstrates the application of electrofused magnesia to castables.

                  TABLE 10                                                         ______________________________________                                         Sample      5A           5B     5C*                                            ______________________________________                                         MgO (wt. %) 99.18        99.44  99.50                                          CaO (wt. %) 0.67         0.45   0.24                                           SiO.sub.2 (wt. %)                                                                          0.05         0.01   0.08                                           ______________________________________                                          *For comparison                                                          

                  TABLE 11                                                         ______________________________________                                                           Sample  Sample  Comparative                                  Example           51      52      Sample 51                                    ______________________________________                                         Formulation (wt. %)                                                            Electrofused magnesia 5A                                                       5-3 mm            15                                                           3-1 mm            30                                                           1-0 mm            20                                                           Electrofused magnesia 5B                                                       5-3 mm                    15                                                   3-1 mm                    30                                                   1-0 mm                    20                                                   Electrofused magnesia 5C                                                       5-3 mm                            15                                           3-1 mm                            30                                           1-0 mm                            20                                           Sintered magnesia fine powder                                                                    30      30      30                                           Alumina cement    3       3       3                                            Silica flour      2       2       2                                            Dispersing agent  +0.1    +0.1    +0.1                                         Physical properties                                                            Bulk density (%)                                                               110° C. × 24 h                                                                      3.03    3.04    3.01                                         1500° C. × 3 h                                                                      3.02    3.01    3.01                                         Apparent porosity (%)                                                          110° C. × 24 h                                                                      16.0    15.8    16.4                                         1500° C. × 3 h                                                                      18.1    18.3    17.9                                         Flexural strength (kg/cm.sup.2)                                                110° C. × 24 h                                                                      38      36      41                                           1500° C. × 3 h                                                                      75      69      83                                           Linear change ratio (%)                                                        1500° C. × 3 h                                                                      -0.42   - 0.35  -0.55                                        Corrosion resistance *                                                                           89      83      100                                          Melt loss index.                                                               ______________________________________                                          * Evaluated by measuring corrosion by slag (CaO/SiO.sub.2 = 3.0) on the        lining of a highfrequency induction furnace at 1650° C. for 5           hours.                                                                   

Castable refractories in Table 11 are obtained by mixing and molding the electrofused magnesia having chemical compositions as specified in Table 10. Each sample contains 5.6% of a casting ingredient. It is noted that samples 51 and 52 pertaining to the present invention are superior in corrosion resistance.

EXAMPLE 6

This example demonstrates the application of electrofused magnesia to refractory ramming materials.

Samples shown in Table 12 were prepared by formulating the samples of Table 10.

                  TABLE 12                                                         ______________________________________                                                           Sample  Sample  Comparative                                  Example           61      62      Sample 61                                    ______________________________________                                         Formulation (wt. %)                                                            Electrofused magnesia 5A                                                       5-3 mm            15                                                           3-1 mm            30                                                           1-0 mm            24                                                           Electrofused magnesia 5B                                                       5-3 mm                    15                                                   3-1 mm                    30                                                   1-0 mm                    24                                                   Electrofused magnesia 5C                                                       5-3 mm                            15                                           3-1 mm                            30                                           1-0 mm                            24                                           Sintered magnesia fine powder                                                                    28      28      28                                           Bittern (32 Be)   +5      +5      +5                                           Silica flour      3       3       3                                            Borax             +0.5    +0.5    +0.5                                         Physical properties                                                            Bulk density (%)                                                               110° C. × 24 h                                                                      2.98    2.99    2.96                                         1500° C. × 3 h                                                                      2.93    2.93    2.89                                         Apparent porosity (%)                                                          110° C. × 24 h                                                                      14.3    14.0    14.8                                         1500° C. × 3 h                                                                      20.0    19.8    20.1                                         Flexural strength (kg/cm.sup.2)                                                110° C. × 24 h                                                                      81      71      86                                           1500° C. × 3 h                                                                      103     92      109                                          Linear change ratio (%)                                                        1500° C. × 3 h                                                                      -0.16   -0.13   -0.20                                        Corrosion resistance *                                                                           84      77      100                                          Melt loss index.                                                               ______________________________________                                          * Evaluated by rotating corrosion test with electromagnetic steel scale a      1450° C. for 30 minutes 10 cycles.                                

Further, the samples of electrofused magnesia shown in Table 12 were mixed by a sand mill into refractory ramming materials for a heating furnace. The sample for quality evaluation was molded under a pressure of 400 kg/cm². It is noted from Table 12 that samples 61 and 62 pertaining to the present invention are superior in resistance to corrosion by electromagnetic steel slag.

INDUSTRIAL FEASIBILITY

(1) The electrofused magnesia of the present invention can be obtained from a magnesia raw material of comparatively low purity. It has a high ratio of single crystal as well as a high CaO/SiO₂ ratio. CaO concentrated on the grain boundary reacts with slag to raise the slag viscosity, thereby preventing the infiltration of slag into the grain boundary. Because of this property, the electrofused magnesia can be used as a filler for refractory bricks to provide good corrosion resistance.

(2) The electrofused magnesia according to the present invention used as a filler improves refractory materials in terms of strength, toughness, and elastic modulus at high temperatures.

(3) The electrofused magnesia can be produced more economically with less electric power than the conventional product if the magnesia raw material is of the same purity.

(4) The electrofused magnesia gives rise to a filler composed of single crystal grains. It contains a trace amount of CaO-SiO₂ in the form of a solid solution, which, during the use of the refractory bricks, separates out to wet the surface of the grains, covering the grains with a highly viscous film on account of the high CaO/SiO₂ ratio. This produces the following two effects.

(a) The film of the high CaO/SiO₂ ratio itself functions as a sintering agent between the grains of the basic filler. In the case of unburned bricks, this promotes sintering of the grains of the basic filler at the temperature of using, imparting to them high strength and high corrosion resistance.

(b) In the case of carbon-containing basic bricks, the highly viscous film of the high CaO/SiO₂ ratio presents in the filler, which covers carbon fine particles, effectively protecting the carbonaceous powder from oxidation.

(5) For reasons mentioned above, the electrofused magnesia will find use as lining bricks, burned or unburned, for high temperature refining furnaces such as converters of high secondary combustion ratio and stainless steel melting furnaces.

(6) Owing to its high ratio of single crystal, the electrofused magnesia will find use as inexpensive optical windows, electronic device substrates, and crucibles of magnesia single crystal, in addition to ordinary refractory materials. 

We claim:
 1. An electrofused magnesia clinker for a refractory material consisting essentially of 98.0 to 99.8 wt. % of MgO, less than 0.05 wt. % of SiO₂, and 0.1 to 2.0 wt. % of CaO.
 2. A refractory material comprising electrofused magnesia clinker consisting essentially of 98.0 to 99.8 wt. % of MgO, less than 0.05 wt. % of SiO₂, and 0.1 to 2.0 wt. % of CaO.
 3. A refractory material comprising electrofused magnesia clinker and 3-40 wt. % of a carbonaceous material, said electrofused magnesia clinker consisting essentially of 98.0 to 99.8 wt. % of MgO, less than 0.05 wt. % of SiO₂, and 0.1 to 2.0 wt. % of CaO.
 4. A refractory material as defined in claim 3 which contains more than 10 wt. % of electrofused magnesia clinker.
 5. The refractory material of claim 2 or 3 which is unburned bricks, burned bricks, and prepared unshaped refractories.
 6. An electrofused magnesia clinker for a refractory material said clinker consisting of crystal containing 98.0 to 99.8 wt. % of MgO, less than 0.05 wt. % of SiO₂, and 0.2 to 1.0 wt. % of CaO.
 7. An electrofused magnesia clinker for a refractory material said clinker consisting of crystal containing 98.0 to 99.8 wt. % of MgO, less than 0.05 wt. % of SiO₂, and 0.2 to 2.0 wt. % of CaO.
 8. An electrofused magnesia clinker for a refractory material said clinker consisting of crystal containing 98.0 to 99.8 wt. % of MgO, less than 0.02 wt. % of SiO₂, and 0.2 to 2.0 wt. % of CaO, in which low-silica periclase crystals have lime which separates on their grain boundary.
 9. A refractory material comprising electrofused magnesia clinker consisting of crystals containing 98.0 to 99.8 wt. % of MgO, less than 0.05 wt. % of SiO₂, and 0.2 to 2.0 wt. % of CaO.
 10. A refractory material comprising more than 10 wt. % of electrofused magnesia clinker consisting of crystals containing 98.0 to 99.8 wt. % of MgO, less than 0.05 wt. % of SiO₂, and 0.2 to 1.0 wt. % of CaO.
 11. A refractory material comprising more than 10 wt. % of magnesia clinker consisting of crystals containing 98.0 to 99.8 wt. % of MgO, less than 0.03 wt. % of SiO₂, and 0.1 to 1.0 wt. % of CaO.
 12. A refractory material comprising more than 10 wt. % of electrofused magnesia clinker consisting of crystals containing 98.0 to 99.8 wt. % of MgO, less than 0.02 wt. % of SiO₂, and 0.2 to 2.0 wt. % of CaO, in which low-silica periclase crystals have lime which separates on their grain boundary.
 13. A refractory material comprising more than 10 wt. % of electrofused magnesia clinker and 3-40 wt. % of a carbonaceous material, said electrofused magnesia clinker containing 98.0 to 99.8 wt. % of MgO, less than 0.02 wt. % of SiO₂, and 0.2 to 2.0 wt. % of CaO in which low-silica periclase crystals have lime which separates on their grain boundary.
 14. A refractory material as in any of claims 9 to 13 which is selected from a group consisting of unburned bricks, burned bricks and prepared unshaped refractory material. 